Methods of implanting dopant ions

ABSTRACT

Methods of implanting dopant ions in a substrate include depositing a sacrificial material on a substrate. Dopant ions are implanted into the substrate while sputtering the sacrificial material, without substantially sputtering the substrate. Substantially no sacrificial material remains on the substrate after the implanting of the dopant ions. Some methods include forming a sacrificial material over a substrate, and implanting dopant ions into the substrate while removing substantially all the sacrificial material from the substrate. Substantially no sputtering of the substrate occurs during the implanting of the dopant ions. Methods of doping a substrate include implanting dopant ions into a substrate having a sacrificial material thereon, and sputtering the sacrificial material while implanting the dopant ions without substantially sputtering the substrate. Substantially no sacrificial material remains on the substrate after implanting the dopant ions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 13/098,607, filed May 2, 2011, pending, which is a continuation of U.S. patent application Ser. No. 11/861,665, filed Sep. 26, 2007, now U.S. Pat. No. 7,935,618, issued May 3, 2011, the disclosure of each of which is hereby incorporated herein by this reference in its entirety.

TECHNICAL FIELD

Embodiments of the invention relate to methods for doping substrates in semiconductor constructions.

BACKGROUND

A continuing trend in the semiconductor industry is increased densification and miniaturization of features. In fabricating semiconductor devices, including resistors, capacitors and transistors, device size must continue to shrink in order to increase the performance and lower the cost of ultra-large scale integrated (ULSI) circuits. Among the components that continue to reduce in scale are junctions, which are doped regions on a wafer where dopants such as boron, phosphorus and arsenic, are implanted into a silicon substrate. The dopants impart desired electrical properties to the wafer by allowing silicon, normally only a semiconducting material, to conduct current. Junctions are used to form source and drain (S/D) regions of MOS transistors. Devices now require shallow junctions, which are formed by implanting ions to shallow depths on the order of about 100-500 angstroms and typically about 300 angstroms or less. The formation of ultra-shallow junctions allows smaller device dimensions and higher circuit density.

Ion implantation is replacing diffusion as the standard technique for introducing conductivity-altering dopant materials into semiconductor wafers in most ULSI doping processes. FIG. 1 schematically illustrates a conventional ion beam implanter 10 for forming doped regions in a wafer 12. In a conventional beam-line type ion implantation system, a desired dopant material is ionized in an ion source 14 to form an ion beam 16, the ions are accelerated to a high velocity using an accelerator 18, and the ion beam 16 is directed at the wafer 12 situated on a wafer chuck 20. The depth to which ions are implanted in the wafer is obtained by controlling the energy of the ions as they impinge on the wafer surface. The beam current in implanters generally ranges between about 1 mA to 30 mA, depending on the implant species, energy and type of implanter. The ions penetrate the surface of the wafer and are embedded into the crystalline lattice of the semiconductor material. The number of implanted ions per unit area, or dose (φ), is related to beam current I (amperes), beam area A (cm²) and implant duration t (seconds), and typically ranges from 10¹¹-10¹⁶ ions/cm². The implanted substrate is subsequently annealed (e.g., at about 900-1,100° C.) in an inert gas (e.g., N₂, etc.) to activate the dopants, i.e., transfer the dopants from impurities to carriers in the crystal lattice.

The reduction of device dimensions, for example, the shortened channel lengths of MOS transistors, creates a so-called short-channel effect (SCE). To minimize the short-channel effect, an ultra-shallow junction depth (x_(j)) and low enough sheet resistance (R_(s)) are required for the source/drain (S/D) fabrication of MOS transistors. For example, for 45 nm technology node based on the International Technology Roadmap on Semiconductor 2005 (ITRS2005), it is required that the junction depth of S/D extension is shallower than 6.5 nm and the activated Rs of S/D extension is lower than 650 Ω/sq. To meet these requirements as device size shrinks, ultra-low energy (e.g., <1 keV for boron) ion implantation must be used.

Conventional beam-line ion implantation offers advantages over traditional diffusion techniques, including (1) precise control of dose and depth profile due to decoupling of the doping and annealing processes; (2) low temperature processing, which allows the use of photoresist as a mask; (3) the ability to use a wide selection of masking material (e.g., metal, polysilicon, photoresist, oxide, etc.); and (4) less sensitivity to surface cleaning procedures. However, despite the advantages of conventional beam-line ion implantation processes, there are several drawbacks relating to fundamental physical limitations such as space charge limits, intrinsic sputtering effects, and implant angle limits for non-planar structures for low energy implants. These limitations create problems in microelectronics manufacturing.

With conventional beam-line ion implantation processes, the ion beam and momentum of the ions impinging on the wafer causes sputtering of the silicon substrate during doping, resulting in the removal of doped silicon material. The sputtering effect by energetic ion bombardment during ion implantation both affects the structure of the devices and the as-implanted dopant profile. Etching, including sputtering and reactive ion etching (RIE), is known to cause retained dose saturation of the dopant and, in turn, sheet resistance (R_(s)) saturation in the wafer. The implant dose in the substrate is removed by etching so that the dose is saturated after the removed depth equals the implant range (Rp).

In FIG. 2, the retained boron dopant dose (atoms/cm²) and sheet resistance (R_(s)) (Ω/sq.) saturations is plotted as a function of nominal B implant dose (ions/cm²) by ultra-low energy (500 ev) boron (B) beam-line ion implants. As shown, the value of R_(s) does not fall below 650 Ω/sq. regardless of the duration (time period) of the ion implantation process (Shu Qin et al., “Measurement and analysis of deposition-etch characterization of BF₃ plasma immersion ion implantation,” Review of Scientific Instruments 73(2): 840-842 (2002)). This demonstrates that for ultra-low energy implants, conventional beam-line ion implantation does not achieve the desired sheet resistance (R_(s)) due to its intrinsic sputtering effect.

It would be useful to provide a method for optimizing bean-line ion implants that overcomes these or other problems.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention are described below with reference to the following accompanying drawings, which are for illustrative purposes only. Throughout the following views, the reference numerals will be used in the drawings, and the same reference numerals will be used throughout the several views and in the description to indicate same or like parts.

FIG. 1 schematically illustrates a conventional ion beam implanter.

FIG. 2 graphically illustrates retained boron (B) dose (atoms/cm²) and sheet resistance (R_(s)) (Ω/sq.) saturations plotted as a function of nominal B implant dose (ions/cm²) (¹¹B⁺ 500 eV, beam-line ion implant, RTP: 1050° C./0 s) (♦=B dose, ▴=R_(s)).

FIG. 3 illustrates a diagrammatic, cross-sectional view of a portion of a substrate at a preliminary processing stage according to an embodiment of the present disclosure.

FIGS. 4-6 are cross-sectional views of the substrate depicted in FIG. 3 at subsequent processing stages according to an embodiment of the invention.

FIGS. 7-10 are cross-sectional views of the substrate depicted in FIG. 3 at subsequent processing stages according to another embodiment of the invention.

FIGS. 11-12 are cross-sectional views of the substrate depicted in FIG. 6 (or FIG. 10) at subsequent processing stages.

FIG. 13 graphically illustrates sputtering yields (atoms/ion) of boron ions on silicon, boron and carbon substrates at B⁺ ion energies between 0 and 2.5 keV based on an ion implantation computer simulation using SRIM2006 software (♦=B⁺ ion on silicon; ▴=B⁺ ion on boron; ▪=B⁺ ion on carbon).

FIG. 14 graphically illustrates sputtering yields (atoms/ion) of arsenic ions (As⁺) on silicon and carbon substrates at As⁺ ion energies between 0 and 2.5 keV based on an ion implantation computer simulation using SRIM2006 software (♦=As⁺ ion on silicon; ▴=As⁺ ion on carbon).

FIG. 15 graphically illustrates typical DIED simulation results assuming 500 eV B⁺ ion implanted on a silicon substrate with a nominal dose of 2e15 ions/cm² and a sputtering rate of 3 angstroms (Å) per 4e13 ions/cm² nominal dose (implant time: 50 seconds, nominal dose/second: 4e13 ions/cm², sputtering/second: 3 Å) (Pearson-4 Profile: Rp=40 Å, Sp=22 Å, skewness=0.5418; kurtosis=2.9763).

FIG. 16 graphically illustrates a comparison of the retained boron (B⁺) ion doses (atoms/cm²) versus nominal B doses (ions/cm²) by DIED simulations for a silicon substrate with no sputtering, a silicon substrate with sputtering, and a silicon substrate with sputtering of an overlying 50 Å boron (B) film (500 eV ¹¹B⁺ beam-line ion implant on silicon).

FIG. 17 graphically illustrates a comparison of the retained B profiles (B concentration in atoms/cm³ versus depth in angstroms) by DIED simulations for a silicon substrate with no sputtering, silicon substrate with sputtering, and silicon substrate with sputtering of an overlying 50 Å boron (B) sacrificial film (500 eV ¹¹B⁺ beam-line ion implant on silicon).

DETAILED DESCRIPTION

The following description with reference to the drawings provides illustrative examples of devices and methods according to embodiments of the invention. Such description is for illustrative purposes only and not for purposes of limiting the same.

In the context of the current application, the term “semiconductor substrate” or “semiconductive substrate” or “semiconductive wafer fragment” or “wafer fragment” or “wafer” will be understood to mean any construction comprising semiconductor material, including but not limited to bulk semiconductive materials such as a semiconductor wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure including, but not limited to, the semiconductive substrates, wafer fragments or wafers described above.

Conventional processes using beam-line ion implantation for doping a silicon substrate cause sputtering of the silicon substrate, which can result in a loss of the implanted dopant material from the substrate layer. Embodiments of the invention optimize ultra-low energy beam-line ion implantation to reduce sputtering of a silicon substrate to be doped by use of a sacrificial material film layer that is pre-deposited onto a silicon substrate surface. Due to the low sputtering yield and optimized thickness of the sacrificial material film, sputtering of the silicon substrate is eliminated and the retained dopant dose and R_(s) saturations are improved. The resulting doped silicon substrate has reduced sheet resistance and improved electrical properties.

An embodiment of a method according to the invention for doping a silicon substrate using an ultra-low energy beam-line ion implantation process is illustrated with reference to FIGS. 3-6. FIG. 3 illustrates a substrate fragment indicated generally with reference to numeral 22 at a preliminary processing stage. The substrate fragment 22 in progress can comprise a semiconductor wafer substrate or the wafer along with various process layers faulted thereon, including one or more semiconductor layers or other formations, and active or operable portions of semiconductor devices.

The substrate fragment 22 comprises a substrate 24 to be doped to a conductivity type and a masking layer 26. The substrate 24 is generally a semiconductor material such as monocrystalline, polycrystalline or amorphous silicon. A typical thickness of the silicon substrate 24 is about 300-800 μm. The masking layer 26, typically photoresist, is formed over the silicon substrate 24, and as depicted, can be exposed and developed using conventional photolithographic techniques. Other mask materials such as silicon dioxide, silicon nitride, carbon, among others, can also be used. The mask 26 provides a desired pattern with openings 28 that define and expose selected areas of the silicon substrate 24 to be doped to form, for example, source/drain (S/D) regions, polysilicon gate, etc.

In accordance with the invention, as shown in FIG. 4, a sacrificial material layer 30 is predeposited (arrows ↓↓↓) onto the silicon substrate 24 (and masking layer 26) prior to ion implantation. The material layer 30 is considered to be a sacrificial layer such that it is consumed during a subsequent ion implantation step. The thickness (t) of the predeposited sacrificial layer 30 is designed and optimized such that the layer 30 is progressively consumed by sputtering effect during the ion implantation and completely (or substantially completely) removed from the substrate 24 by the end of the implantation process. The presence of the sacrificial layer 30 substantially eliminates sputtering of the substrate 24 during the ion implantation process to reduce the loss of implanted dopant (through sputtering) and provide an increased retained dopant dose in the silicon bulk.

The material selected for the sacrificial material layer 30 possesses a lower sputtering rate or yield than the silicon substrate 24 and is compatible with the ions to be implanted and the implantation process that is used for implanting the ion species. The sacrificial material is selected so that byproducts resulting from sputtering of layer 30 during the ion implantation processing do not contaminate the substrate or form impurities that would be incorporated into the silicon substrate 24 and adversely affect the nature and/or functioning of the doped substrate. Other factors considered in the selection of the material for the sacrificial layer include low particle generation, ease of formation and processing, reasonable cost and process integration compatibility.

The material layer is composed of the same species or dopant type (e.g., n- or p-type) as the dopant being implanted, or other material that is compatible with the dopant and silicon substrate, to eliminate contamination and not adversely affect the character of the doped substrate. For example, in embodiments in which p-type dopants (e.g., boron, etc.) are ion implanted in a silicon substrate 24, the sacrificial material layer 30 can be formed from a carbon material (e.g., amorphous carbon, silicon carbide (SiC), etc.), or from a boron (B) material (e.g., boron (B), boron carbide (B₄C), silicon boride (SiB₆), etc.) where boron (B) is implanted. In embodiments in which n-type dopants (e.g., phosphorus, arsenic, etc.) are ion implanted, the sacrificial material layer 30 can be formed from a carbon material, or from a phosphorus (P) or arsenic (As) material where P or As, respectively, are implanted. A boron or carbon film used as a sacrificial layer produces only about one-third of the sputtering yield of a silicon substrate. In addition, carbon is an electrically neutral material if incorporated into silicon, and thus does not adversely affect the doped silicon substrate. The sacrificial material layer can be analyzed by known techniques, for example, by transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD).

The sacrificial material layer 30 can be formed on the silicon substrate 24 by various processes known in the art. For example, the sacrificial material layer can be vapor deposited in a processing chamber by atomic layer deposition (ALD), plasma doping deposition (PLAD), chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), or other vapor deposition process. The use of ALD or PLAD deposition methods to form the sacrificial material layer provides acceptable controllability and repeatability in the nanometer regime of deposition processing.

Generally, in an ALD process, one or more precursor gas source gases are pulsed into a deposition chamber for a selected time period (pulse duration), the gases are vaporized and chemisorb as a monolayer onto the substrate, and a number of consecutive deposition cycles are conducted to deposit thin layers (e.g., about 0.2-3.0 Å per cycle) until a layer of the desired thickness is built up on the substrate. In a PLAD process, which is conducted under deposition conditions, reaction gases can be fed into a reactor where an energy source generates a plasma and the gas species react and deposit as a layer onto the surface of the substrate. In a CVD or PECVD process, a source gas or combination of gases is fed into a reaction chamber where the gases react and thermally decompose on a heated substrate.

In embodiments of the invention, a sacrificial material layer 30 of boron, phosphorus or arsenic can be formed by a vapor deposition process using a hydride gas such as diborane (B₂H₆), tetraborane (B₄H₁₀), phosphine (PH₃), arsine (AsH₃), or others, in an inert carrier gas (e.g., argon, helium, nitrogen). The layer 30 can be deposited in a single step or in multiple steps to achieve a desired thickness.

In another embodiment, boron carbide (B_(x)C) can be deposited as the sacrificial material layer 30 in a vapor deposition process (e.g., ALD, CVD, PECVD) using a boron gas precursor such as diborane (B₂H₆), tetraborane (B₄H₁₀) or boron trichloride (BCl₃), and a carbon-forming precursor (e.g., CH₄, C₃H₈, C₃H₆, etc.), as described, for example, in US 2006/0001175 (Sandhu et al., Micron Technology Inc.). For example, a boron carbide (B_(x)C) layer can be vapor deposited from a gas mixture of B₂H₆/CH₄ or BCl₃/CH₄/H₂ or B₂H₆/B₄H o/borane carbonyl (BH₃CO).

In other embodiments, a silicon carbide (SiC) layer can be formed as the sacrificial material layer 30 by vapor deposition using a silicon gas precursor such as silane (SiH₄), in combination with a carbon-forming precursor, e.g., a SiH₄/hydrocarbon gas mixture, as described, for example, in US 2002/000444 (Goela et al.; CVD SiC) and US 2006/0046345 (Akram et al., Micron Technology, Inc.).

Vapor deposition processing (e.g., CVD, PECVD) can also be used to form a sacrificial material layer 30 of an amorphous carbon (or transparent amorphous carbon) using one or more hydrocarbon process gas such as propylene (C₃H₆), methane (CH₄), acetylene (C₂H₂), ethylene (C₂H₄), ethane (C₂H₆), propane (C₃H₈), etc., as described, for example, in U.S. Pat. No. 7,220,683 (Yin, et al.) and US 2006/0001175 (Sandhu et al.) (Micron Technology, Inc.).

A boron sacrificial material layer can also be formed by physical vapor deposition (PVD) by sputtering (sputter vapor deposition) using solid (pure) boron or a solid boron compound such as boron carbide (B₄C) as the sputter target, as described for example, in U.S. Pat. No. 5,672,541 (Booske et al.) and US 2006/0032525 (Olsen et al). Briefly, in a sputter vapor deposition, a silicon substrate (wafer) is inserted into a vacuum chamber, ions are generated and directed at a sputter target material, and the sputtered atoms are deposited as a layer on the substrate.

In another embodiment, the sacrificial layer can be formed by thermal spraying (e.g., plasma spraying) a material layer onto the substrate. Boron carbide, for example, can be deposited using thermal spray techniques, as a plasma spray generated from a powdered material (e.g., a high-purity B₄C) that is heated in a high-temperature gas stream (e.g., plasma gas) to above its melting point, as described, for example, in U.S. Pat. No. 6,808,747 (Shih et al.). The heated, high velocity gas and entrained molten powder strike the substrate to be coated and the molten powder solidifies on contact with the substrate to form a coating of the powdered material.

Referring now to FIG. 5, using conventional beam-line ion implantation (arrows ↓↓↓), the unmasked sections of the silicon substrate 24 are then doped to a p-type or n-type conductivity and a selected dose using a dopant species 32 that is compatible with or of the same type species as used for the sacrificial material layer.

The energy used is determined by the desired depth of the implant. In some embodiments, the ion implantation is conducted at an ultra-low energy range, e.g., to form a shallow junction, typically about 500 eV to about 1 keV using an ultra-low energy ion implanter (sub-2 keV). The amount of dopant ions that is implanted is effective to provide a low sheet resistance (R_(s)). For example, an implant dosage of about 1e14-1e16 ions/cm² at a beam energy of about 0.2-2 keV is typically used. For a shallow junction source/drain (SD) application, a dose of at least about 1e15 ions/cm² or higher is typical.

The profile of the implant can be predicted using a variety of computer simulation tools that conduct ion implantation process simulations for a semiconductor device to determine an ion implantation profile. For example, computer simulation techniques using known software such as SRIM and TRIM packages can be used for modeling the ion implantation process to achieve the appropriate implant conditions and dose amounts. For example, the depth and profile of an ion implant species can be estimated by using SRIM2000 (Stopping Range of Ions in Matter), a widely available simulation program that calculates the depth and distribution of ions implanted into materials and takes into account the density of the material being implanted and the energy and mass of the impacting species. A SRIM simulation program can also be utilized to simulate and calculate the sputtering rates for different ion species with different energies on different substrates.

Sputtering of the sacrificial material layer 30 occurs as the ion implantation proceeds, resulting in a continuous decrease in the thickness (t) of the sacrificial material layer 30. The sacrificial layer is predeposited on the silicon substrate 24 to a pre-designed thickness to maintain a film over the silicon substrate until the completion of the ion implantation. The thickness (t) of the predeposited layer 30 is optimized and controlled based on the implantation of a defined dose so that the layer is completely expended (used up) at the end or completion of an implantation step to implant the defined dose, and essentially none of the sacrificial layer remains, as illustrated in FIG. 6.

As illustrated in FIGS. 3-6, in some embodiments, the sacrificial layer 30 is predeposited onto the silicon substrate to a calculated thickness (t) in a single application, and the defined dosage is then ion implanted in one step (FIG. 5), with sputtering completely removing the layer 30 from the substrate at the end of the implantation process (FIG. 6). The optimal required thickness of the sacrificial material layer 30 for complete removal by self-sputtering by the end of the implantation process can be calculated and determined based on factors such as the sputtering yield data or sputtering rate of the sacrificial material, the ion implantation species, the nominal dose amount that is applied, and process conditions such as the implant energy.

In embodiments of the invention in which the sacrificial layer 30 is deposited and the entire defined dosage is then ion implanted, the thickness of the predeposited sacrificial material layer 30 is typically about 40-60 angstroms. For example, in the use of a boron (B) sacrificial material layer 30 for implanting boron (B) ions 32 at a low implant energy of 500 eV, based on a sputtering rate of the boron sacrificial layer of about 1 Å per 4e13 ions/cm² nominal dose and a required nominal boron dose of 2e15 ions/cm², the deposit of an about 50 Å sacrificial boron layer will maintain a sacrificial boron film over the silicon substrate for the duration of a beam-line ion implantation to implant the identified dose without sputtering of the silicon substrate, with the layer 30 being completely removed from the substrate at the end of the implant.

In another embodiment of the invention, illustrated in FIGS. 7-10, the ion implantation can be conducted in two or more stages to implant portions of the total defined dose amount, with the sacrificial material layer being predeposited before each implanting step. Again, the thickness (t) of the sacrificial material layer is calculated according to the dose that is implanted and the sputtering yield of the sacrificial material. For example, for implanting an about 1e15 atoms/cm² dose of boron ions 32′ (of a total boron dose of 2e15 ions/cm²) in a first step, a first sacrificial layer 30 a′ with a thickness (t₁) of about 25 Å can be deposited as depicted in FIG. 7, which thickness will maintain the sacrificial layer 30 a′ on the silicon substrate 24′ to the completion of the first implanting step (FIG. 8). Then, prior to implanting the remaining 1e15 ions/cm² boron dose, a second sacrificial layer 30 b′ with a thickness (t₂) of about 25 Å can be pre-formed on the partially doped silicon substrate 24′ as depicted in FIG. 9, which will maintain a film on the silicon substrate to the completion of the second implanting step (FIG. 10), whereupon the sputtering effect from the ion implantation process will have completely removed the layer 30 b′ from the substrate.

In embodiments of the invention in which multiple sacrificial layers 30 a′, 30 b′ are deposited and a portion of the defined dosage is then ion implanted after each such deposition, the thicknesses (t₁, t₂) of each of a first and second pre-deposited sacrificial layer 30 a′, 30 b′, for example, are typically about 20-30 angstroms. For example, in the use of a boron (B) sacrificial material layer 30 for implanting boron (B) ions 32, based on an implant energy of 500 eV, a sputtering rate of the sacrificial layer of about 1 Å per 4e13 ions/cm² nominal dose, and a 1e15 ions/cm² nominal dose for each implant step, the deposit of an about 25 Å sacrificial boron layer for each implant step will maintain a sacrificial boron film over the silicon substrate for the duration of a beam-line ion implantation to implant the identified 1e15 ions/cm² nominal dose without sputtering of the silicon substrate, with each of the sacrificial layers 30 a′, 30 b′ being completely removed from the substrate at the end of each of the implant steps.

Referring now to FIG. 11, after the ion implantation process is completed, the photoresist mask layer 26 and/or other masking material can be selectively removed (stripped) with wet chemical or dry etching or a combination of both. Photoresist, for example, can be removed by a standard dry etch process using an oxygen (O₂) plasma ashing step. Optionally, the silicon substrate 24 can be treated by dry or wet etching to expose and clean the surface and remove any remaining residue of the sacrificial material layer and/or masking material.

As depicted in FIG. 12, the doped substrate 24 can then be annealed (arrows ↓↓↓) to activate the implanted dopant ions 32, for example, using a rapid thermal anneal process at a temperature of about 900-1100° C., to form a shallow junction 34, for example. The ion dose (implanted and annealed) can be measured by a SIMS technique, and the sheet resistance (R_(s)) can be measured by a four point probe technique, using conventional techniques.

The described process results in a reduction of the implanted dopant loss caused by sputtering of a silicon substrate during beam-line ion implantation, an increase in the retained dopant dose in the silicon bulk, improvements in the R_(s) saturation, and no or minimal structural change of the original substrate surface.

Embodiments of the invention can be used to produce shallow junctions, polysilicon gates, etc., with required junction depth (X_(j)) and sheet resistance (R_(s)). The doped substrate 24 can undergo additional processing steps known in the art to fabricate desired components. Finished semiconductor wafers can be cut into dies, which may then be further processed into integrated circuit chips and incorporated in electronic devices.

EXAMPLES

To illustrate the process of the invention, sputtering of various materials situated on a silicon substrate and the ion implantation of boron (B) and arsenic (As) ions in a silicon substrate using a pre-deposited sacrificial material layers were investigated.

Compared to n-type impurities such as As or P, boron (B) ion species are more critical for ultra-low energy implant applications due to the lower mass (severe space charge effect), much lower solid solubility than n-type impurities, segregation behavior, and the intrinsically lower mobility of holes (thermally activated from boron impurity) than electrons.

Table I lists the sputtering yields (at atoms/ion) of boron ions (B⁺) and arsenic ions (As⁺) on different substrates which are III- or IV-family impurity materials, versus the B⁺ and As⁺ ion energy ranging from 200 ev to 2 keV.

TABLE I Sputtering Yield by SRIM2006 Simulations Ion Energy 200 eV 500 eV 700 eV 1 keV 1.5 keV 2 keV Sputtering Sputtering Sputtering Sputtering Sputtering Sputtering Yield Yield Yield Yield Yield Yield Substrate (atoms/ion) (atoms/ion) (atoms/ion) (atoms/ion) (atoms/ion) (atoms/ion) B⁺ on Si 0.5474 0.7717 0.8318 0.8987 0.9512 0.9368 B⁺ on B 0.1682 0.2647 0.3038 0.3281 0.3785 0.3798 B⁺ on C 0.1705 0.2633 0.2803 0.307 0.3304 0.3493 B⁺ on Al 0.6976 0.9586 1.06 1.13 1.2 1.19 B⁺ on Ga 0.51 0.8579 0.9962 1.14 1.22 1.3 B⁺ on In 0.3869 0.7668 0.8981 1.03 1.2 1.22 B⁺ on Ti 0.235 0.7264 0.8819 1.08 1.24 1.34 As⁺ on Si 0.1152 0.3529 0.4821 0.6493 0.8826 1.07 A_(s) ⁺ on C 0.0122 0.0896 0.135 0.208 0.3202 0.4246

FIG. 13 illustrates the sputtering yields (atoms/ion) of boron ions on silicon, boron and carbon substrates versus the B⁺ ion energy (keV). FIG. 14 illustrates the sputtering yields (atom/ion) of arsenic (As⁺) ions on silicon and carbon substrates versus the As⁺ ion energy (keV).

The sputtering yield data for Tables I-II and FIGS. 13-14 was based on an ion implantation computer simulation using SRIM2006 software (J. F. Ziegler, http://www.SRIM.org/). Of the listed materials, boron (B) and carbon (C) were chosen for further study due to their lower sputtering yield, being about one-third the sputtering yield of a silicon substrate in an energy range of 200 eV to 2 keV.

Table II (below) lists the sputtering yield or rate data (at Å/sec) of boron (B⁺) and arsenic (As+) ions implanted on different substrates (silicon, boron, carbon) versus the implant energy at 200 eV, 500 eV and 1 keV. The data are based on Table I and assumes that the doping rates of the impurities at all energies (i.e., nominal doping rate) are fixed at 4e13 cm²/sec, and the sputtering rate of 500 eV B⁺ ions implanted on silicon substrates is 3 Å/second.

TABLE II Sputtering Rate Data (Assume the Nominal Doping Rate is 4e13/cm²-sec) 200 eV 500 eV 1 keV Ion Energy (Å/sec) (Å/sec) (Å/sec) B⁺ on Si 2.13 3 3.5 B⁺ on B 0.64 1 1.2 As⁺ on Si 0.447 1.37 2.52 As⁺ on C 0.048 0.35 1.09

An ion implantation simulator DIED (Dynamic Ion-implantation with Etching and Deposition) was used to determine the final retained boron (B) profile/dose when sputtering or deposition effects were included. A DIED simulator is a MATLAB®-based software that iteratively computes the retained implanted dopant profile, dose, and maximum concentration including the etching (sputtering or RIE) and deposition effects. The impurity profiles of DIED use Pearson-IV profile function (J. F. Ziegler, http://www.SRIM.org/), which is a more accurate function than simple symmetrical Gaussian function.

FIG. 15 illustrates a typical DIED simulation result assuming 500 eV B⁺ ion implanted on a silicon substrate with a nominal dose of 2e15 ions/cm² and a sputtering rate of 3 Å per 4e13 ions/cm² nominal dose. The doping rate was 4e13 ions/cm²-sec, so that the total implant time was 50 seconds for 2e15/cm² nominal dose. Due to the sputtering effect, the retained B profile becomes half Gaussian-like function, the retained B dose is saturated at about 7e14 atoms/cm², and the maximum concentration is saturated at about 1.9e21 atoms/cm³.

The results show that a boron (B) film can be pre-deposited as a sacrificial film to reduce the sputtering effect to about one-third of the sputtering yield of a silicon substrate, and improve the retained dose loss issues caused by sputtering effects during the ion implantation. Assuming that a boron (B) substrate has a sputtering rate of 1 Å per 4e13 ions/cm² nominal dose, for a nominal dose of 2e15 ions/cm², it will take about 50 seconds to complete the implant during which about 50 Å of the B substrate will be removed by sputtering effect. In an embodiment of the invention, an about 50 Å boron (B) film can be pre-deposited on a silicon wafer surface as a sacrificial layer so that when the ion implantation is completed, the sacrificial B film is concurrently and completely removed by the self-sputtering action by the end of the ion implantation process. The B dose loss from the silicon bulk by sputtering effect can thus be reduced.

FIG. 16 illustrates a comparison of the retained boron (B⁺) ion dose (atoms/cm²) versus nominal B dose (ions/cm²), and FIG. 17 illustrates retained B profiles by DIED simulations for a silicon substrate with no sputtering, silicon substrate with sputtering, a silicon substrate with an overlying pre-deposited 50 Å boron (B) sacrificial film, and an embodiment (discussed below) in which a 2e15/cm² nominal dose implant is performed in two steps with each implant step involving a pre-deposit of a 25 Å boron (B) film and implanting half of the nominal dose (i.e., 1e 15/cm²). The results show that when there is no sputtering effect, the retained B dose equals the nominal B dose (FIG. 16), and the final B profile is a Pearson-IV function with a higher maximum concentration (FIG. 17). FIG. 17 also demonstrates a high level of agreement of boron (B) profiles between DIED simulation and SRIM2006 simulation.

A comparison of the results of sputtering a silicon (Si) substrate with sputtering a boron (B) sacrificial film situated on a silicon (Si) substrate according to embodiments of the invention shows a significant improvement on retained B dose and maximum concentration saturations. The results indicated that the retained B dose did not reach saturation and is about double to that of silicon (Si) substrate at a nominal dose of 2e15 ions/cm² with a 77% retained dose increase (FIG. 16).

In another embodiment, the implant process can be divided into multiple steps, with a sacrificial material layer deposited prior to each implant step. For example, a 2e15 ions/cm² dose implant can be divided into two steps by pre-depositing a 25 Å boron (B) sacrificial film and ion implanting one-half of the required nominal dose (i.e., 1e15 ions/cm²), with the sacrificial film being completely removed by self-sputtering at the end of the first implant step. A second 25 Å boron (B) sacrificial film can then be pre-deposited and the remaining half of the required nominal dose (i.e., 1e15 ions/cm²) ion implanted, wherein the second sacrificial film is also completely removed by self-sputtering from the doped silicon substrate at the end of the second implant step.

As illustrated in FIGS. 16-17, the use of a multiple step (e.g., two-step) implant process using multiple pre-formed 25 Å boron (B) sacrificial layers provided a higher retained boron (B) dose and maximum ion concentration compared to a one-step boron (B) implant process using a single pre-formed 50 Å boron (B) sacrificial film. The results also show that the retained B⁺ dose increased by 127% compared to the B⁺ dose resulting from a conventional implant process of a silicon (Si) substrate without the use of a sacrificial layer.

Table III (below) lists the simulation results of retained boron (B⁺) dose, retained boron (B⁺) dose fraction (retained B dose/implant nominal B dose), and process improvements (B⁺ dose increase) of B⁺ ion implants at different energies when the exposed substrate is silicon (Si) (conventional implant process), and by a sputtering-less implant processing according to embodiments of the invention using a boron (B) sacrificial film substrate over silicon by a one-step and by a two-step deposition/implant process (based on an implant nominal B dose of 2e15 ions/cm²). With sputtering-less implant processing according to the invention, the retained boron doses can be increased from about 77% to up about 244% depending upon the implant energies and processing embodiment (i.e., 1-step or multi-step) that are used.

TABLE III Retained B Dose and Retained B Dose Fraction (Retained Dose/Nominal Dose) and Improvement by Sputtering-less Implant; Implant Nominal B Dose is 2e15/cm² 200 eV 500 eV 1 KeV Ion Energy (/cm²) (/cm²) (/cm²) B⁺ implant Retained 7.459E+14 7.459E+14 4.915E+14 on Silicon Dose Fraction 37.30% 37.30% 24.58% Improvement NA NA NA One time B⁺ Retained 1.892E+15 1.323E+15 1.323E+15 implant on Dose Silicon with Fraction 94.60% 66.17% 66.17% sacrificial Improvement 153. 62%  77.40% 169.20%  B film Two time B⁺ Retained 1.892E+15 1.692E+15 1.692E+15 implant on Dose Silicon with Fraction 94.60% 84.59% 84.59% sacrificial Improvement 153.62%  126.77%  244.14%  B film

Methods of the invention utilize a sacrificial material layer that provides a lower sputtering rate than the substrate to be implanted, resulting in an improvement (i.e., reduction) of the sputtering effect of low energy ion implants on the dopant-implanted substrate. Sacrificial material layers utilized according to the methods of the invention are removed by self-sputtering during the ion implantation process, which eliminates the need to remove the sacrificial material after the ion implant is completed, thereby reducing the number of required processing steps. By comparison, other materials such as oxides (e.g., SiO₂) that have a similar sputtering rate as silicon (Si) do not improve or reduce the sputtering effect of low energy ion implants, and must also be removed after the process has been completed.

Some embodiments of the invention, for example, utilize a boron or carbon sacrificial layer for a boron (B⁺) ion implantation, and a carbon sacrificial layer for an arsenic (As⁺) ion implantation. Advantages of using carbon (C) as the sacrificial material layer (or a boron (B) layer in the case of a boron implant) compared to other materials include a lower sputtering yield than silicon, no contamination of the silicon substrate, less particle generation, compatibility to the ion implant, and ease of processing the material to form the sacrificial layer (e.g., by ALD, PLAD, etc.).

Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations that operate according to the principles of the invention as described. Therefore, it is intended that this invention be limited only by the claims and the equivalents thereof. The disclosures of patents, references and publications cited in the application are incorporated by reference herein. 

1. A method of implanting dopant ions in a substrate, comprising: depositing a sacrificial material on a substrate; and simultaneously implanting dopant ions into the substrate and sputtering the sacrificial material without substantially sputtering the substrate, wherein substantially no sacrificial material remains on the substrate after the implanting of the dopant ions.
 2. The method of claim 1, wherein depositing a sacrificial material on a substrate comprises depositing the sacrificial material by vapor deposition.
 3. The method of claim 2, wherein depositing the sacrificial material by vapor deposition comprises utilizing a process selected from the group consisting of atomic layer deposition, plasma doping deposition, chemical vapor deposition, and plasma enhanced chemical vapor deposition.
 4. The method of claim 2, wherein depositing the sacrificial material by vapor deposition comprises consecutively depositing a plurality of layers of the sacrificial material over the substrate.
 5. The method of claim 2, wherein depositing the sacrificial material by vapor deposition comprises exposing the substrate to at least one of a hydride gas, a boron gas precursor, a silicon gas precursor, and a hydrocarbon gas.
 6. The method of claim 1, wherein depositing a sacrificial material on a substrate comprises thermally spraying the sacrificial material on the substrate.
 7. The method of claim 1, wherein simultaneously implanting the dopant ions into the substrate comprises implanting from about 1×10¹⁴ ions/cm² to about 1×10¹⁶ ions/cm² into a surface of the substrate.
 8. The method of claim 1, wherein simultaneously implanting the dopant ions into the substrate comprises implanting boron ions, phosphorus ions, or arsenic ions into the substrate.
 9. The method of claim 1, wherein simultaneously implanting the dopant ions into the substrate comprises simultaneously implanting the dopant ions at a beam energy of from about 0.2 keV to about 2.0 keV.
 10. The method of claim 1, wherein sputtering the sacrificial material comprises continuously decreasing a thickness of the sacrificial material.
 11. The method of claim 1, further comprising: forming another sacrificial material on the substrate after implanting the dopant ions; and simultaneously implanting additional dopant ions into the substrate and sputtering the another sacrificial material.
 12. The method of claim 1, wherein simultaneously implanting the dopant ions into the substrate and sputtering the sacrificial material comprises simultaneously implanting a p-type dopant into the substrate and sputtering a carbon material or a boron material.
 13. The method of claim 1, wherein simultaneously implanting the dopant ions into the substrate and sputtering the sacrificial material comprises simultaneously implanting an n-type dopant into the substrate and sputtering a carbon material, a phosphorous material, or an arsenic material.
 14. The method of claim 1, wherein depositing a sacrificial material on a substrate further comprises: forming a patterned mask on the substrate to expose a portion of the substrate; and depositing the sacrificial material on the exposed portion of the substrate.
 15. The method of claim 14, further comprising removing the patterned mask after implanting the dopant ions.
 16. A method of doping a substrate, comprising: forming a sacrificial material over a substrate; and implanting dopant ions into the substrate while removing substantially all the sacrificial material from the substrate, wherein substantially no sputtering of the substrate occurs during the implanting of the dopant ions.
 17. The method of claim 16, further comprising: forming another sacrificial material over the substrate after implanting the dopant ions; and removing substantially all the another sacrificial material from the substrate while implanting additional dopant ions into the substrate, wherein substantially no sputtering of the substrate occurs during the implanting of the additional dopant ions.
 18. The method of claim 16, wherein forming a sacrificial material over a substrate comprises forming the sacrificial material by a process selected from the group consisting of atomic layer deposition, plasma doping deposition, chemical vapor deposition, and plasma enhanced chemical vapor deposition.
 19. A method of doping a substrate, comprising: implanting dopant ions into a substrate having a sacrificial material thereon; and sputtering the sacrificial material while implanting the dopant ions without substantially sputtering the substrate, wherein substantially no sacrificial material remains on the substrate after implanting the dopant ions.
 20. The method of claim 1, wherein implanting dopant ions into a substrate comprises implanting the dopant ions into a substrate comprising monocrystalline silicon, polycrystalline silicon, or amorphous silicon. 